Electrical capacitor



March 29, 1960 F. J. P. JQ BURGER ETAL 2,930,951

ELECTRICAL cAPAcIToR Filed July 8, 1957 FAQ( 7' Imnfrs,

Franc/'5d P al Bagger; Hari* H. .Uf/fr?,

The/'r' J-frny.

The present invention relates to. electrical capacitors,

f rUnited .Statespmro Francis I. P. Burger and H. Hilton, Glens N.Y., assignorsto .General Electric Company,- a cor- 2,930,951y Patented Mar. 29, 1960 '-relates to an- 'electrical' capacitor comprising a first electrodelayer', a. thin anodic dielectric oxide layer'overlyf ing a major portion of the surface of the first electrode layer, a second anodic oxide film overlying a minor por tion of the surface of the first electrode layer, the second .anodicoxide ilm being 'substantially thicker than the '.rstanodicoxide'layer, and a second electrode layer overlying 'both anodic oxide layers and spaced thereby l from'the first electrode layer. l0

`The thicker oxide layer described provides mechanical and electrical reinforcement in the termi-nal contact refand lmore particularly to an-improved dry type electrical* capacitor and method of producing the same.

' 'Conventional electroll c capacitors utilizing liquid 'h lelectrolytes haveseveral drawbacks, largely d'ue to the possibility ofleakage or evaporation of the contained' electrolyte. -Escape of the electrolyte' frequently'leads to' deterioration of the operating efiiciency ofthe capac'ition `of both-thi:l dielectric layers, the diferent thicknesses being 'obtainedby .selective formation of the dielectric.'

.layers in different' types of film-forming electrolytes.

tor, results in `corrosion ofthe casing Aand other metal parts, and causes other detrimental efects.-

I` o avoid these difficulties, severalattempts have been made inthe past to construct solid, dry typesofcapaci-v tors whereinone electrode is a filming metal on which an oxide film is anodically formed to serve as the capaci- -Jtor dielectric, and an electrically conductive layer' is deposited over the dielectric oxide tlm to serve as the second electrode.' The priortypes of such solidcapacipractice for a variety of' reasons. A principal difficulty encountered is the problem 'of making a secure electrical A and mechanical connection betweenthe thin deposited,

' lpartying drawing, in which;

- tors, however', have not been found fullysatisfactory in electrode layer and the conducting lead. Previously at- ',j 'tempts 'at solving this difficulty have included .the use 'of organic or synthetic resins as reinforcing materials for f Athe terminal contact area, or the use 'of metal reinforcement, e.g., solder or the like, in this area. Buttthese modifications did not in genreal prove suitable, since the organicy .reinforcement materials failedat elevated temperature, and the application of metalreinforc'ement material frequently caused vshort circuits* at theterrninal rekgion duel to the extremel thinness of the dielectric film separating the two-electrodes. The provision of thicker' dielectric films to overcome this drawback would not effectively solve the problem, since increasing the st'rength of the dielectric film -by making it thicker would be at the cost of corresponding reduction of the 'capacitance of the device. i It 'is an object of the invention to providean improved electricall capacitor which overcomes the -above disadvantages of known types vof capacitors,

It is another object of the invention to provide a solid, dry type electrical capacitor having high electrical eiciof operating conditions which is ency over a wide range .economical to produce.

It isa'further object'V ofthe inventionto provide an .electrical capacitor of the above type having an -improved gion where a"c'on"ductive lead may be securely attached to the .capacitor device in good electrical connection with t.he'- second electrode layer, which is normallyin the form `of averythin conductive coating'. At the same time, the thin," dense oxide layer over a major portion of the device serves 'to produce high capacitance in the capacitor without'being-subjected to the stresses required for good electrical connection'of the leads to the electrodes. A significant feature of the invention is the anodic forma- The invention will be'better understood from the fol-- I lowing description taken im conjunction with the accom- Fig. l is a plan view of an embodiment of acapacitor device'constructed 'in accordance with the present iriwmibn;

Pig. v2 is a cross-sectional view inexaggerated scale of the Fig. 1 device taken along the line 2-2;

Fig. 3 'is'a' cross-sectional view of the' Fig. 1 device taken along -the lline 3'-3; A

- ,Fig 4 is -a cross-sectional view of a modification of the Fig. 1 device;

' Fig. Seis a view -of the device which includes one form 4of moisture .impervious enclosure;`

. Fig. 6 is 'a view, partly broken away, of the present device including a different form of moisture impervious enclosure;-and Fig 7 shows a multiple unit arrangement incorporatl ing'capacitor units constructed in accordance with the invention. Referring now to a the drawnig, and particularly to Figs.v l- 3 there is shown a solid, dry type capacitor unit A constructed in accordance with the invention, which cornpriss a plate 1 of aluminum serving as one electrode of the capacitan" Preferably, the aluminum of which platel 1 is composed of" is of high-purity and desirably though.

thereon.,

not necessarily is of at least 99.97% pure aluminum. In-

stead of -being of' solid aluminum, thebase plate 1 may be of any suitable material havinga coating of aluminum Formedover the mai-or portion of the' surface of elec trode plate 1 is a thin, anodically deposited, aluminum oxide Adielectric film 2, with an end portion 1 of .plate 1' being leftfree of oxide'lm to serve as the terminal region for electrode plate 1. Over-the opposite terminal I end portion of the capacitor device as shown, there is terminalstruc-ture whichensu'res good `electrical conneco tion to the respective electrodes of! the capacitor "while f stituting the principal `dielectric layer of the capacitor.

avoidingI electrical breakdown of the terminal contact areas. i

lt is still method of making electrical capacitors of the above type 'which isreadilyand economically carried out and which another object ofthe invention to provide a provides. any improved terminal vstructure without sacri-l fice ofthe electricaleflicieticyof the capacitor.4

Other objects and advantages will become apparent from the following description and the appended claims.

formed a second anodic oxide layer 3 whichis relatively "thick, hard, porous' aluminum oxide .material, as com pared to theverythin,l dense aluminum oxide film 2 con- Deposited over the oxide llayers 2 and 3 is a thin metallic layer 4 which maybe of the 'same aluminum composition ofthe plate-electrode 1, or any other suitable `conductingimateial such as tin, silver, cop'per, lead', zinc or non-metallic solid conductive materials such as carbon and may be applied by any metallizing; or othersuitable With the above objects infview, the present invention depositing procedures. A satisfactory metal'coating may be produced, for'example, by vacuum evaporation of the .desired metal, or by sputtering, dipping, painting, chemical deposition, or the like.

The carbon 'electrode layer may be formed by applying a coating of a dispersion of finely divided graphite, such as by painting or dipping and thereafter drying and baking the coating. This provides a particularly economical method of forming the outer electrode. As shown the end portions of oxide dielectric film 2 are left free of the metal electrode material 4 by the use of suitable masking means such as a coating of varnish wax or shield to avoid the possibility of a short circuit between the two electrodes.

Lead 5 is firmly secured in electrical connection with electrode plate 1 by rivet 6 or the like which passes through the uncoated terminal portion of plate 1. Lead 7 is similarly connected to electrode layer 4 by rivet 8 and washers 9, 9', the latter elements being interposed in direct contact with electrode layer 4 as shown in Fig. 3. As is evident from Fig. 3, the aperture for rivet 8 is made in plate 1 prior to subjecting the electrode plate to the described film forming and metallizing procedures so that rivet 8 is separated from the electrode plate 1 by the superposed oxide and metal coatings and thereby prevented from .causing a short circuit between the electrodes.

The thicknesses of the layers of the device illustrated are shown iu exaggerated scale for the purposes of clarity, and the relative dimensions of the parts as shown, except as otherwise specifically mentioned, are not necessarily those used in practice. In a practical device, the thicknesses of the various parts may typically be as follows: electrode plate 1, 40 mils; thin dielectric oxide film 2, 1 to 2 microns; thick porous oxide film 3, 30 microns; and the metal electrode layer 4, 0.3 micron.

Of particular significance is the provision in accordance with the invention of the two different oxide layers 2 and 3. each having characteristics designed to meet their particular function in the capacitor. Oxide layer 3 is deposited in the terminal region i.e., where the lead 7 t to be fixed, by anodizing this portion of the plate 1 .n a solution of film-forming electrolyte inY which the anodic aluminum oxide film is somewhate soluble. Such electrolytes are, for example, oxalic acid, dilute sulfuric acid, and sulfamic acid. Although the reaction between such film-forming electrolytes and the aluminum oxide film formed thereby is not completely known, it appears that the oxide layer is porous as it is being formed, due presumably to its partial solution in the electrolyte. Because of its porous nature, the film permits continued penetration of the electrolyte to the surface of the aluminum plate 1 for further reaction therewith so as to increase the thickness of the aluminum oxide film being formed.

On the other hand, the thin dielectric oxide layer 2 is formed in accordance with conventional capacitor electrode film-forming procedures whereby a very thin, dense anodic oxide layer is produced on the surface of the electrode. The forming electrolytes used for this purpose may comprise, for example, boric acid, tartaric acid, phosphoric acid and salts thereof, glyco-borates, or citric acid, or such other known film-forming electrolytes as have little or no solvent action on the aluminum material of the electrode plate. The film formed by such electrolytes is a non-porous, dense barrier-type layer, and after being formed to a certain extent, the film resists further oxide formation (anodization) necessitating constantly increasing voltages to produce further anodic reaction. In addition to the above differences, the relatively thick aluminum oxide layer 3 further is found to be substantially stronger and much more resistant to abrasion than the thin dielectric oxide film 2.

By providing a relatively thick hard oxide such as constituted by layer 3 at the terminal portion, a thicker metallized electrode layer can be deposited over that portion while avoiding danger of subsequent electrical breakdown at that point, and because it is thicker at the terminal contact point, the metallized layer is less Subject to burning away (clearing) which would cause an open circuit there. This is especially desirable since at this point concentration of the current is relatively high, especially under clearing conditions.

Since the main dielectric layer 2 need not in view of the above contribute to reinforcement of the terminal region, it may be formed in an extremely thin film thereby increasing the capacitance of the capacitor. The conducting electrode 4 deposited overlying a suitable portion of the previous dielectric layers may be made sufficiently thin to enable clearing of conducting faults in the dielectric films by local vaporization or oxidation of the deposited electrode layer 4 when a suitable voltage is applied. Such clearing may occur under actual operating conditions.

Preferably the terminal oxide layer 3 is produced in a wedge form with the thin end gradually tapering into and merging with the main dielectric layer 2. This configuration ensures a smooth transition point on which the metallic layer 4 may be uniformly deposited and there by avoids an irregular base which may be difficult to properly metallize and which might result in a gap in the electrode layer or a region susceptible to electrical breakdown.

The following is a typical method of producing capacitors of the described construction in accordance with the present invention it being understood that the invention is in no way limited by the specific process or compositions set forth. It is desirable to initially properly clean and polish the surfaces of the base aluminum sheet especially around the edges ofthe sheet and of the rivet receiving apertures. Before the anodizing treatment is initiated the electrode plate may be etched in accordance with known processes to increasethe effective area of the sheet. The thus treated sheet is then made the anode in an aqueous forming bath of about'3% oxalic acid with only the terminal end portion immersed in the bath for forming the thick terminal oxide portion. To form the desired wedge shape of this oxide portion the electrolyte solution is preferably agitated to produce a ripple in the bath, which results in the tapering formation sought, or the sheet may be gradually withdrawn from the electrolyte. Typically, a D.C. voltage between 50 and 100 volts is applied in this forming step for a sufficient period to produce the desired thickness of the aluminum oxide film.

Following this treatment and after being rinsed, the sheet is then anodized in an aqueous 10% boric acid solution with the entire specimen immersed except for the opposite, previously unanodized terminal end portion (region 1'). The forming voltage used in this procedure may be increased to a voltage of, say, 500 volts, while the current is allowed to drop from an initial value of about 500 milliamps, the formation being continued until a minimum leakage current is attained, after which the specimen is rinsed and ready for metallizing.

As will be observed from the drawing, the thin barriertype dielectric layer 2 forms over the maior portion of the aluminum sheet in contact with the latter even in the region of the previously formed thick terminal oxide layer 3 with which it appears to become integrated. This occurs because the boric acid electrolyte is able, due to the porosity of the thick oxide layer 3, to penetrate the latter and reach the aluminum electrode plate l at its base to react therewith and anodically form on its surface the thin barrier layer 2.

The thus anodized aluminum sheet is then exposed to a metallizing operation, e.g., by exposing both sides to vacuum evaporation of high purity aluminum, care be ing taken to mask suitably the end portion of the unit so that the metal coating 4 extends short of the end of the thin oxide coating 2. A suitable minimum coating density for the metallized layer has been found to be about 0.6 to 0.8 mg. per square inch of actual surface areal covered.. Thinner pacitance which decrcasesgradually 'The lead wires are thereafter preferably secured 'by "means .of rivets, asshown 4in the drawing,- or equivalentwith time.

What we'c'laim for actual' contact to the metallizedlayer 4,. and

` f since' iti is important to ensurethatther'e'me no burrsor i -sharp edges on the'washers, the latter elementsjare sub- Ajected to a polishing treatment' similar t`o that` usedfoi" 4after assembly, it.is desirable to by applyingna D.C. voltage' rising' in steps to a desired44 overlying onlyj said claims intended to cover all such equivalent varia- .Y

tions aseomewithin the true spirit and scope of the in# vention.

Patent of theUnited States is;

1 -1. An'electri lcapacitor. comprising a trst aluminum I electrode Alayer Ahaving-a Afirst terminal portieri, a thin A anodic alilmiiium oxide dielectric layer overlying a maior aluminum portion ofthesurface of' s aid. 511i electrode layer, a second anodic aluminum oxide dielectric layer n first terminal ,portion of the surface I of 'said lirstalumi-num electrode layer, said 'second oxide vl f diel c'layer beingatleastseveral times thicker thanv said'rst'oxide dielectiiclayen' a second electrode layer Y overlying: both' said oxide tlielectriclayers and spaced.

."thei'eby-frorn said first aluminum' electrode' layer, said tion is not limited to such connecting means.. The lead wires may, for. example, merely be suitably wound or clamped around the terminal portions of the *capacitor without rivets or teminal apertures -being provided `as- --showm or any other suitable lead 'connectingmeans such as' soldering or the like may be used.

v oltage.

The device described above may be further modied, if desired, as shown in Fig. 4 by interposing a layer of a semi-conducting oxide material '10, such as`MnO3, be# tween the thin aluminum oxide dielectric layer 2a and the outer metalliied; electrode -layer 4a. Experiments indicate that the use of such intermediate layer of semi` conductive oxide material may enable thecapacitor to' withstand higher operating voltages andincrease -the'- .stability of capacitance and power factor characteristics.' .For full efliciency under operating conditions where yr'noistui'e may`be a factor, it is preferable that the resent capacitor de vice. be protected f rmthe action o water vap'or. To this -end the device maybe encapsulatecl'or enclosed by a suitable outer protective'rneans.. .In one -form, as shown in Fig. 5, the device may be provided with outer enveloping coating 1 1-of a suitable mois. ture impervious composition having a thickness, say, of

the order of 40 mils. Silicone resin qcoating compounds' are particularly suitable for this. purpose, especially where high operating temperatures are encountered, but

various other'known types of moisture impervious coating materials such as polyethylene glycol .t'erephthallate resin or-epoxy resin may be used where appropriate.

Alternatively, the capacitor may be enclosed as shown lin Fig. 6, hermetically `sealed within 'a suitable moisture impervious container 12 made of metal, glass, ceramic or other rnaterial, the capacitor assembly being suspended on' its opposite leads which pass through end-discsuidtightly sealing the interior'of the container.

The disclosed capacitor device may be used as a single unit AL as shown in Figs. 1 6, or' a plurality of such clear the.4 `capacitor :nal-portion, a thin,

` layer overlying 30' aluminum sheet a 'second' anodic aluminum oxide dieleclayer in the region of tirst electrode layer having 'an uiicoated lsecond terminal "portion, and means for securing leads in electrical con nection'to said iirst aluminuinelect'rode layer at its un- Vcoated terminal port ion and to said second electrode" said-second anodic oxide dielectric^ layer, whereby said thicker'. 4oxide layer provides substa'nt'ial resistanceagainst mechanical and electrical stress to .avoid electrical breakdown at said first terminal por- 25 v l i '2. An electrical capacitor'comprising a sheet of alu-- minum'constituting a iirst electrode having 4a lirst termidenseanodic aluminum oxide dilectric a maior portion of opposite sides of said tric' layer superposed on said thin oxide layer only on said tirst terminal portion of oppositesides of said alumif num sheet'saidsecond anodic oxide dielectric layer being porous -and at`least several times thicker than said thin,

units. A may be assembled with the'units connected in4 parallel or in series. Fig. 7 -shows a. parallel assemblyof stacked units connected by rivets 14, 15. If necessary,

metallic inserts may be placed between the adjacentv lelectrode portions for '-better, electrical contact between the units.

' the scopeof the invention..

While. shown ,in lthe form of rigid elongated'rectangu;

' constituting dense anodic oxide dielectric layer, a metallized layer constituting a second electrode on opposite sides of said aluminumsheet overlying both said oxide dielectric'layers and spaced thereby from said first electrode, and means for securing conducting leads in electrical connection to said aluminum sheet and to 'said metallized layer in the region'of said thicker-anodic oxide dielectric layer, whereby said thicker Voxide layer. provides substantial resistance against`mechanical and electrical stress to avoid electrical breakdown vatfsaid first terminal portion.

3, An electrical capacitor comprising a sheet of aluminum constituting arst electrode having a lirst terminal portion, athn dense anodic aluminum oxide dielectric layer overlying a major portion of opposite sides of said 'aluminumsheet -a second anodic aluminum oxide dielectric layer supcrposed on said thin oxide layer only on said first terminal portion of opposite sides of said aluminum .sheetsaid second anodic oxide layer being'` p orous and at least several times thicker than said thin,

dense anodic oxide dielectric layer, `a metallized layer asecond ele'ctro'de o n opposite sides of said aluminum -sheet)overlying bothsaid oxide dielectric layers -and spaced thereby from said lirst electrode, said aluminum sheet having an uncoatedsecond terminal portion, and meansl for. securing conducting leads in electrical connection to said electrodes, said means comprising fas- 4tenirig means passing through s aiduncoated lterminal porti'on of said aluminum sheet and through the assembly lar plate, the capacitor.'1 unit may h emadel in other forms l without going 'beyond the scope of the presentinvention;

.. "For" example, plates ofany desired thickness ,vor contiguration may be used, or'the capacitor may be a yflexible sheet in hat, cylindrical, or helically or convolutely wound condition, or it may b'e inthe f orm ofl a wire (coiled or shaped), and the metal used maybe sintered, 'etched or in otherfo'rms which increase the effective area.

While the present'inven'tion has been described with understood .that 'numeousmoditications may -be made by those'skilled inthe art without actually departing from Therefore, the Aappended reference to particularcmbodiments`thereof, it willbe of layers in the region of said second anodic oxide layer, whereby 'said thicker oxide 'layer proyidessubstantial resistance'against mechanical and electrical stress to avoidl electrical breakdown at said trsttern'tinal portion.

' 4. An electrical capacitor comprising a sheet of aluminum 'constituting a rst electrodeA having a first terminal.

dense anodic .aluminum oxide dielectric 'layer overlying 'a major poi-tionA of opposite sides of `said aluminum's'heet, a second anodic aluminum oxide jportion, a thin,

on said first terminalp'ortion ofopposite sides of said 'aluminum'sheet, said second anodic .oxide layer being porous and at least several times thicker than said thin,

as new 'a'nd-desir'e by Letters.

dielectric layer superposed on .said thin oxide layer vonly denseanodic oxide dielectric layer, a metallized layer constituting a second electrode on opposite sides ofsaid aluminum sheet overlying both said oxide dielectric layers and spaced thereby from said rst electrode, means for securing conducting leads in electrical connection to said aluminum sheet, and to said metallized layer in the region of said thicker anodc oxide dielectric layer, and enclosing means enveloping and hermetically sealing the assembly of layers, whereby said thicker oxide layer provides substantial resistance against mechanical and electrical stress to avoid electrical breakdown at said rst terminal portion.

5. A device as dened in claim 4, wherein said enclosing means is constituted by a moisture-irnpervious coating enveloping said assembly of layers.

6. A device as delined in claim 4, wherein said enclosing means is constituted by a moisture-impervious container.

7. An electrical capacitor comprising, in combination, an assembly of electrically connected capacitor units, each capacitor unit comprising a sheet of aluminum constituting a iirst electrode having a lrst terminal portion, a thin, dense anodc aluminum oxide dielectric layer overlying a major portion of opposite sides of said aluminum sheet, second anodc aluminum oxide dielectric layer superposed on said thin oxide layer only on said first terminal portion of opposite sides of said aluminum sheet, said second anodic oxide layer being porous and at least several times thicker than said thin, dense anodc oxide 4dielectric layer, a thin conducting layer constituting a second electrode on opposite sides of said aluminum sheet overlying both said oxide dielectric layers and spaced thereby from said rst electrode, said aluminum sheet having an uncoated second terminal portion, and means for holding said units in assembly and for securing leads in electrical connection to the electrodes thereof, said means including fastening means in contact with at least certain ofvsaid units in the region of the second anodic oxide layer thereof, whereby said thicker oxide layer prdvides substantial resistance against mechanical and electrical stress to avoid electrical breakdown at said rst terminal portion.

8. An electrical capacitor comprising a iirst aluminum electrode layer having `a tirst terminal portion, a thin anodc aluminum oxide dielectric layer overlying a major portion of the surface of said first aluminum electrode layer, a layer of semi-conductive material composed of manganese dioxide superposed on said thin dielectric layer, a second anodc aluminum oxide dielectric layer superposed on said thin oxide layer only overlying said first terminal portion` of the surface of the first aluminum electrode layer, said second anodic aluminum oxide dielectric layer being at least several timesA thicker than said first mentioned dielectric layer, and a second electrode layer overlying both said dielectric layers and spaced thereby from said first aluminum electrode layer, whereby said thicker oxide layer provides substantial resistance against mechanical and electrical stress to avoid electrical breakdown at said rst terminal portion.

References Cited in the tile of this patent UNITED STATES PATENTS 1,923,539 Jenny et al Aug. 22, 1933 1,965,683 Work July 10, 1934 2,052,575 Lilienfeld Sept. 1, 1936 2,076,904 Lilienfeld Apr. 13, 1937 2,079,516 Lilienfeld May 4, 1937 2,174,840 Robinson et al. Oct. 3, 1939 2,174,841 Robinson Oct. 3, 1939 2,578,400 Cohn Dec. 11, 1951 FOREIGN PATENTS 873,672 France July 16, 1942 746,584 Germany Aug. 30, 1944 

